CN108369982A

CN108369982A - Wavelength conversion body, wavelength converting member and light-emitting device

Info

Publication number: CN108369982A
Application number: CN201680065675.1A
Authority: CN
Inventors: 奥野达也; 中村将启; 李柔信; 藤井俊平
Original assignee: Panasonic Intellectual Property Management Co Ltd
Current assignee: Panasonic Intellectual Property Management Co Ltd
Priority date: 2015-12-11
Filing date: 2016-12-09
Publication date: 2018-08-03
Also published as: US20200255729A1; JPWO2017098730A1; WO2017098730A1; JP6688973B2; EP3389100A1; EP3389100A4

Abstract

The wavelength conversion body (1) of the present invention has：Multiple fluorophor particles (10)；With adhesive layer (20), the adhesive layer is by multiple average grain diameter D₅₀Nano-particle adhesion body made of nano-particle adhesion for 1nm less than 100nm forms and adjacent fluorophor particle (10) is made to stick to each other.The preferred average grain diameter D of nano-particle₅₀It is 10nm less than 100nm.Fluorophor particle (10) preferably comprises following fluorophor particles：By after the firing of 1200 DEG C or more of fluorophor particle in an atmosphere brightness divided by an atmosphere brightness maintenance rate obtained from the brightness before the firing of 1200 DEG C or more of fluorophor particle be 80% or less.

Description

Wavelength conversion body, wavelength converting member and light-emitting device

Technical field

The wavelength conversion body of luminescence generated by light is the present invention relates to the use of, even more particularly to illuminated high-power sharp It heat resistance and thermal diffusivity is also excellent and productivity is excellent wavelength conversion body, wavelength converting member and shines in the case of shining Device.

Background technology

In the past, as the wavelength conversion body using luminescence generated by light, it is known to by luminous more by the irradiation by exciting light Wavelength conversion body made of the adhesive of these multiple fluorophor particles of a fluorophor particle and holding.It is known that having The wavelength conversion body of fluorophor is filled in organic siliconresin.Wavelength conversion body for example takes following forms：It is formed in metal Lamina on oxide or metal substrate or plate body.

In recent years, for wavelength conversion body, in order to improve optical output power, it is desirable that the high power of exciting light.Therefore, right In wavelength conversion body, as exciting light, gradually become using the high-power exciting light such as laser light source.But organic siliconresin The heat resistance and thermal diffusivity of equal organic bonds are insufficient.Therefore, swash if irradiated to the wavelength conversion body with organic bond The high-power exciting light such as radiant, the then transmission for will produce discoloration in the organic substance for forming adhesive, burning and making light Rate reduces, and thus the light output efficiency of wavelength conversion body is easily reduced.In addition, if to the wavelength convert with organic bond Body irradiates the high-power exciting light such as laser light source, then the thermal conductivity of organic substance would generally be down to less than 1W/mK, therefore meeting Fever.So, the wavelength conversion body with organic bond is easy to happen the temperature quenching of fluorophor.

Existing technical literature

Patent document

Patent document 1：Japanese Patent No. 5090549

Patent document 2：Japanese Unexamined Patent Publication 2015-38960 bulletins

Invention content

Problems to be solved by the invention

It is to be obtained using following compositions to be sintered in this regard, disclosing a kind of wavelength conversion body in patent document 1 's：Heat resistance, thermal diffusivity and the high ceramic material of transmission of visible light；The organic bonds such as organic siliconresin；And fluorophor.It should The wavelength conversion body of patent document 1 is for example manufactured by being sintered at a high temperature of 1200 DEG C or so.But patent The wavelength conversion body of document 1 is due to being to be sintered at high temperature, and there are the low such projects of productivity.In addition, drilling color Property is excellent and fluorophor i.e. CASN ((Sr, Ca) AlSiN for being widely used as the fluorophor of White LED₃：Eu) fluorescence Body will produce oxidation reaction under high temperature environment, and brightness maintenance rate is easy to significantly reduce.Therefore, because being sintered at high temperature The wavelength conversion body of patent document 1 can not use and will produce the CASN fluorophor of oxidation reaction under high temperature environment, therefore deposit It is being difficult to that color rendering is made to improve such project.In addition, the sintered body of the ceramic material such as YAG is arrived greatly due to general refractive index 1.8, therefore there are the light extraction efficiencies of output light to reduce, spot diameter expands such project.

In addition, a kind of method of manufacture light-emitting device is disclosed in patent document 2, using fluorophor and by silica The adhesive that based material or its precursor are formed, cured adhesive sticks to each other fluorophor by being heated at 500 DEG C or less. But since thermal conductivity is usually as low as less than 1W/mK silica compared with other metal oxides, there are wavelength Project as the poor radiation of conversion body.Further, since silica to the refractive index of visible light greatly to 1.5 or so, therefore The projects related with optical characteristics such as there are the light extraction efficiencies of output light to reduce, spot diameter expands.

So, even previous heat resistance and thermal diffusivity, light in the case of illuminated high-power exciting light Extraction efficiency is also excellent and productivity is excellent wavelength conversion body and used the wavelength conversion body wavelength converting member and Light-emitting device is unknown.

The present invention is carried out in view of the above subject.Even the object of the present invention is to provide one kind illuminated Heat resistance and the wavelength convert that thermal diffusivity, optical characteristics are also excellent and productivity is excellent in the case of high-power exciting light Body, wavelength converting member and light-emitting device.In addition, can be described below about optical characteristics.

Means for solving the problems

In order to solve the above problems, the wavelength conversion body of the 1st scheme of the invention is characterized in that having：Multiple fluorescence Body particle；And adhesive layer, the adhesive layer is by multiple average grain diameter D₅₀For 1nm less than the nano-particle adhesion of 100nm and At nano-particle adhesion body formed and so that the adjacent fluorophor particle is sticked to each other.

In order to solve the above problems, the wavelength converting member of the 2nd scheme of the invention is characterized in that having：Substrate；With The wavelength conversion body being formed on the substrate.

In order to solve the above problems, the light-emitting device of the 3rd scheme of the invention is characterized in that, uses the wavelength convert Body or the wavelength converting member obtain white light.

Description of the drawings

Fig. 1 is the wavelength conversion body of the 1st~the 3rd embodiment and the wavelength converting member comprising these wavelength conversion bodies The skeleton diagram of section.

Fig. 2 is the schematic of the wavelength conversion body of the 1st embodiment and the wavelength converting member comprising the wavelength conversion body Cross-section diagram.

Fig. 3 is the schematic cross-sectional view for indicating the part A amplifications of Fig. 2.

Fig. 4 is an example of scanning electron microscope (SEM) photo of the plane of disruption of the wavelength conversion body of embodiment 1 Son.

Fig. 5 is an example of transmission electron microscope (TEM) photo of the part B of Fig. 5.

Fig. 6 is the scanning electron microscope (SEM) as the fluorophor particle of the raw material of the wavelength conversion body of embodiment 1 One example of photo.

Fig. 7 is an example of the chart of the pore-size distribution of the nanovoids 27 for the wavelength conversion body for indicating embodiment 1.

Fig. 8 is the schematic of the wavelength conversion body of the 2nd embodiment and the wavelength converting member comprising the wavelength conversion body Cross-section diagram.

Fig. 9 is the plane of disruption in the case of making the line B-B of wavelength conversion body approximately along Fig. 8 of the 2nd embodiment be broken Scanning electron microscope (SEM) photo an example.

Figure 10 is the schematic of the wavelength conversion body of the 3rd embodiment and the wavelength converting member comprising the wavelength conversion body Cross-section diagram.

Figure 11 is that the wavelength conversion body of the 3rd embodiment as shown in fig. 10 and the wavelength comprising the wavelength conversion body turn Change an example of scanning electron microscope (SEM) photo of the plane of disruption comprising high radiating part 50 in component.

Figure 12 is the section of the wavelength conversion body of the 4th embodiment and the wavelength converting member comprising the wavelength conversion body Skeleton diagram.

Figure 13 is the schematic of the wavelength conversion body of the 4th embodiment and the wavelength converting member comprising the wavelength conversion body Cross-section diagram.

Figure 14 is scanning electron microscope (SEM) photo for the planar exit facet 2 for indicating section shown in Figure 13 An example.

Specific implementation mode

Hereinafter, being illustrated to the wavelength conversion body of present embodiment, wavelength converting member and light-emitting device with reference to attached drawing.

[the 1st embodiment]

(wavelength converting member)

Fig. 1 is the wavelength conversion body of the 1st~the 3rd embodiment and the wavelength converting member comprising these wavelength conversion bodies The skeleton diagram of section.Wavelength conversion body 1A, 1B of 1st~the 3rd embodiment are identical with the skeleton diagram of the section of 1C, therefore together It is shown in Figure 1.In addition, separately including the section of wavelength converting member 100A, 100B and 100C of wavelength conversion body 1A, 1B and 1C Skeleton diagram it is identical therefore shown in Figure 1 together.

As shown in Figure 1, wavelength converting member 100 (100A, 100B and 100C) has substrate 80 and is formed in Wavelength conversion body 1 (1A, 1B and 1C) on the substrate 80.Wavelength converting member 100 (100A, 100B and 100C) is in a substrate There are one wavelength conversion bodies 1 (1A, 1B and 1C) for setting on 80 surface.If a wave is arranged on the surface of a substrate 80 Long conversion body 1, then the manufacture of wavelength converting member 100 is easy.

(substrate)

Substrate 80 is following substrates：Wavelength conversion body 1 to being formed in surface carries out reinforcement, and passes through material and thickness Selection and assign suitable optical characteristics, thermal characteristics to wavelength conversion body 1.

As substrate 80, such as glass substrate, metal substrate, ceramic substrate can be used etc..In addition, substrate 80 can have Translucency can not also have translucency.In the case where substrate 80 has translucency, becoming can be via substrate 80 to wavelength Fluorophor particle 10 in conversion body 1 irradiates exciting light.In addition, in the case where substrate 80 does not have translucency, becoming can be with Exciting light and shining from wavelength conversion body 1 is set to be reflected by substrate 80.

(wavelength conversion body)

The wavelength conversion body and wavelength converting member of 1st embodiment are illustrated.As shown in Figure 1, wave Long conversion body 1A (1) is formed with planar exit facet 2 on the surface with 80 opposite side of substrate.Here, so-called planar exit facet 2 Refer in the surface with 80 opposite side of substrate of wavelength conversion body 1, highly approximately reach identical face.Shown in Fig. 1 Wavelength conversion body 1 for, in addition to the section near the left and right end portions in Fig. 1 be arc-shaped part other than be formed with it is planar Exit facet 2.

As described later, there is wavelength conversion body 1 adjacent fluorophor particle 10 to be obtained each other by 20 adhesion of adhesive layer Structure.Therefore, the surface of wavelength conversion body 1, that is, planar exit facet 2 becomes the tool mainly formed by fluorophor particle 10 There is the male and fomale(M＆F) 3 of minute asperities.Here, so-called male and fomale(M＆F) 3 refers to the face for being unsatisfactory for Ra≤0.15 μm or Rz≤0.3 μm.It needs Illustrate, in Fig. 1, for convenience of description, male and fomale(M＆F) 3 is more emphatically indicated than reality.

Fig. 2 is the schematic of the wavelength conversion body of the 1st embodiment and the wavelength converting member comprising the wavelength conversion body Cross-section diagram.As shown in Figure 2, the wavelength that wavelength converting member 100A has substrate 80 and is formed on the substrate 80 turns Change body 1A.The adhesive layer that wavelength conversion body 1A has multiple fluorophor particles 10 and adjacent fluorophor particle 10 is made to stick to each other 20.Adhesive layer 20 is by multiple average grain diameter D₅₀Nano-particle made of nano-particle adhesion for 1nm less than 100nm is viscous Disjunctor is formed.

In addition, in wavelength conversion body 1A shown in fig. 2, by the surface of each fluorophor particle 10 by adhesive layer 20 It is coating, so as to form the coating fluorophor particle of the nano-particle that is formed by fluorophor particle 10 and adhesive layer 20 30.In addition, wave As long as long conversion body 1A adhesive layers 20 are formed in the way of so that adjacent fluorophor particle 10 is sticked to each other.Cause This can also pass through the surface of each fluorophor particle 10 as the embodiment other than wavelength conversion body 1A shown in Fig. 2 A part it is not coating and expose by adhesive layer 20, to be formed without the wavelength to form the coating fluorophor particle of nano-particle 30 Conversion body.

As long as fluorophor particle 10 is capable of the particle of luminescence generated by light, type is not particularly limited.As fluorescence Body particle 10, such as can be used by YAG, that is, Y₃Al₅O₁₂The particle of the crystal of the garnet structure of formation, by (Sr, Ca) AlSiN₃： The fluorophor particle that Eu is formed.

Fluorophor particle 10 preferably comprises following fluorophor particles：1200 DEG C or more of fluorophor particle in an atmosphere Brightness (L after firing₂) divided by the brightness (L before the firing of 1200 DEG C or more of fluorophor particle in an atmosphere₁) obtained from it is bright Spend sustainment rate (L₂/L₁) it is 80% or less.If fluorophor particle 10 includes brightness maintenance rate (L₂/L₁) it is 80% below glimmering Body of light particle can then be realized with high conversion efficiency and the high wavelength conversion body of color rendering, therefore preferably.

The grain size for the fluorophor particle 10 for including in wavelength conversion body 1A is not particularly limited, for example, 1~100 μm.

Fluorophor particle 10 can be the particle formed by the fluorophor of same composition, can also be what two or more was formed The mixture of the particle of fluorophor.

Adhesive layer 20 is following layer：By multiple average grain diameter D₅₀It is 1nm less than (10 angstroms or more and low of 100nm In 1000 angstroms) nano-particle adhesion made of nano-particle adhesion body formed, and adjacent fluorophor particle 10 is made to glue each other Even.Here, so-called nano-particle adhesion body refers to the nano-particle winner with molecular separating force adhesion each other.In addition, so-called nanometer Particle refers to average grain diameter D₅₀It is 1nm less than the particle of 100nm.The average grain diameter D of nano-particle₅₀Such as pass through TEM (transmission electron microscope), SEM (scanning electron microscope), FE-SEM (field emission type scanning electron microscope) and survey It is fixed.

The average grain diameter D of nano-particle₅₀It is 1nm less than 100nm, preferably 10nm is less than 100nm, more Preferably 10nm is less than 50nm, and further preferably 15nm is less than 25nm.

If the average grain diameter D of nano-particle₅₀It is 1nm less than 100nm, then nano-particle each other can be with intermolecular Power adhesion and form the adhesive layer 20 firmly formed by nano-particle adhesion body, adjacent fluorophor particle 10 each other be easy quilt Consumingly adhesion.

In addition, if the average grain diameter D of nano-particle₅₀Be 10nm less than 100nm, then can inhibit due in order to The underbead crack of adhesive layer 20 caused by manufacture of wavelength conversion body 1A etc. and thermal expansion, thermal contraction when being heated 46 generation.It should be noted that can be described in detail in the 2nd embodiment for underbead crack 46, so-called underbead crack 46 Refer to length formed in adhesive layer 20 be 10 μm or more, the gap that groove width is 2 μm of channel-shaped below.There are inside to split In the case of line 46, underbead crack 46 is typically found in 20 inside of adhesive layer and by the fluorophor grain of adhesion via adhesive layer 20 In the fluorophor particle encircled area 40 that son 10 is surrounded.In addition, underbead crack 46 it is believed that will not to wavelength conversion body 1A and Wavelength converting member 100A causes harmful effect optically.For its reason, can be illustrated in the 2nd embodiment.

As described above, if the average grain diameter D of nano-particle₅₀It is 10nm less than 100nm, then can inhibit inside The generation of crackle 46 can further increase the thermal diffusivity of wavelength conversion body 1A, improve film-strength.Especially in high power density The light-emitting device of excitation is easy to apply in the light-emitting device in the environment of impacting, due to requiring high heat dissipation to wavelength conversion body 1A Property, high film-strength, therefore the average grain diameter D of nano-particle₅₀Preferably 10nm is less than 100nm.

Fig. 3 is the schematic cross-sectional view for indicating the part A amplifications of Fig. 2.The part A of Fig. 2 indicates adjacent fluorophor grain 10 part of adhesion via the adhesive layer 20 formed by nano-particle adhesion body each other of son.Fig. 3 is Jie to the part A of Fig. 2 The figure that the adhesive layer 20 formed by nano-particle adhesion body between fluorophor particle 10 is described in detail.

As shown in Figure 3, the adhesive layer 20 between adjacent fluorophor particle 10 is by multiple nano-particles 21 It is formed each other by nano-particle adhesion body made of molecular separating force adhesion.In addition, constituting the nanoparticle of nano-particle adhesion body Son 21 is also adhered to by molecular separating force on fluorophor particle 10.Nano-particle adhesion body is played adjacent fluorophor as a result, The effect for the adhesive layer 20 that particle 10 sticks to each other.

In addition, as shown in Figure 3, adhesive layer 20 is coating by the entire surface on the surface of fluorophor particle 10.In addition, Adhesive layer 20 need not be coating by the entire surface on the surface of fluorophor particle 10 as shown in Figure 3, as long as by fluorophor The surface of the fluorophor particle 10 of the part only between adjacent phosphor body particle 10 in the surface of particle 10 is coating. That is, as long as adhesive layer 20 is coating by at least part on the surface of fluorophor particle 10.

In addition, if adhesive layer 20 is coating by the entire surface on the surface of fluorophor particle 10, then fluorophor particle is can inhibit 10 is poor with external index step, it is possible to improve absorptivity, the external quantum efficiency of fluorophor particle 10, therefore preferably.Separately Outside, if adhesive layer 20 is only by a part of coating of the surface of fluorophor particle 10, the light being enclosed inside fluorophor particle Ingredient increase, it is possible to make output facula diameter narrowization, therefore preferably.

As shown in Figure 2, in wavelength conversion body 1A, by adjacent 10 portion enclosed of fluorophor particle Middle formation fluorophor particle encircled area 40.Here, so-called fluorophor particle encircled area 40 refers to by adjacent fluorophor Particle 10 is each other by 20 adhesion of adhesive layer, to by 10 area defined of fluorophor particle of adhesion via adhesive layer 20. In addition, via adhesive layer 20 and the fluorophor particle 10 of adhesion can be formed with adhesive layer 20 on the surface of fluorophor particle 10, Adhesive layer 20 can not also be formed.

Fluorophor particle encircled area 40Aa, 40Ab, 40Ac and 40Ad of wavelength conversion body 1A shown in Fig. 2 is wrapped respectively Emptying aperture 45 in the gap, that is, adhesive for being 1 μm or more containing the aperture in above-mentioned adhesive layer 20.In addition, wavelength shown in Fig. 2 turns It changes body 1A and shows the example for all containing emptying aperture 45 in adhesive in whole fluorophor particle encircled area 40.But As the embodiment other than wavelength conversion body 1A, it can also be formed in a part for fluorophor particle encircled area 40 and not wrap The wavelength conversion body of structure containing emptying aperture in adhesive 45.At least part of fluorophor particle encircled area 40 is not included The embodiment of emptying aperture 45 can illustrate in aftermentioned 2nd embodiment in adhesive.

Here, emptying aperture 45 refers to gap that the aperture that is enclosed in adhesive layer 20 is 0.3 μm or more in so-called adhesive. Thus, for example the part other than adhesive layer 20 is formed by gap, is less than 0.3 μ in the gap of 20 split shed of adhesive layer, aperture The gap of m is not included in adhesive in emptying aperture 45.In addition, the shape that so-called aperture refers to the emptying aperture 45 in by adhesive assumes Diameter in the case of for perfect sphere.The aperture of emptying aperture 45 is usually 5~15 μm or so in adhesive.

The shape of emptying aperture 45 is not particularly limited in adhesive, but generally spherical.The length-width ratio of emptying aperture 45 in adhesive (minor axis is length) is usually 1：1~1：10.In addition, for convenience's sake, in Fig. 2 and aftermentioned Fig. 8,10,13, will bond The shape representation of emptying aperture 45 is the shape that section is triangle in agent.For emptying aperture 45 in actual adhesive, due to viscous Close layer 20 mutual bonding part be in necking down and with radian, therefore in adhesive emptying aperture 45 easily become it is spherical.

Emptying aperture 45 impacts the scattering of the visible light in wavelength conversion body 1A in adhesive.For example, if being easy production Emptying aperture 45 is more in adhesive layer 20 in the adhesive that the aperture of raw visible light scattering is 0.3 μm~20 μm, then wavelength conversion body The scattering of visible light in 1A becomes more.In this case, since the waveguide ingredient in wavelength conversion body 1A is easy to increase, have The spot diameter of output light may be made to increase, therefore not preferably.

On the other hand, if emptying aperture 45 exists in the adhesive that the aperture for easy ting produce visible light scattering is 0.3 μm~20 μm Less in adhesive layer 20, then the scattering of the visible light in wavelength conversion body 1A tails off.In this case, due to wavelength conversion body 1A In waveguide ingredient easily reduce, therefore have the effect of improving light extraction efficiency, make output facula diameter narrowization, therefore it is excellent Choosing.

Therefore, wavelength conversion body 1A preferably by via adhesive layer 20 and fluorophor that the fluorophor particle 10 of adhesion is surrounded At least part of particle encircled area 40 does not include empty in the adhesive in the gap that the aperture in adhesive layer 20 is 0.3 μm or more Hole 45.If at least part of fluorophor particle encircled area 40 does not include emptying aperture 45 in adhesive, wavelength conversion body 1A In waveguide ingredient easily reduce, therefore light extraction efficiency can be improved, become easy and make output facula diameter narrowization, therefore is excellent Choosing.

It, each other can be with molecular separating force adhesion and the transmission of exciting light using nano-particle as the material of nano-particle The high inorganic material of property.As the material of nano-particle, aluminium oxide (Alumina), silica, oxidation can be used for example Titanium, zinc oxide, zirconium oxide, boron nitride.The mutual molecular separating force of nano-particle of these materials is strong, is easy to be formed by firmly receiving The adhesive layer 20 that rice corpuscles adhesion body is formed.As nano-particle, can use by a kind or 2 kinds in above-mentioned material with On material formed nano-particle.

In addition, the material of nano-particle is preferably greater than 1W/mK, more preferably greater than 4W/mK in 25 DEG C of thermal conductivity.Separately Outside, the material of nano-particle is preferably shorter than 50W/mK, more preferably less than 30W/mK in 25 DEG C of thermal conductivity.If nanoparticle Within the above range, then the thermal diffusivity of wavelength conversion body 1A is got higher thermal conductivity of the son at 25 DEG C.For example, aluminium oxide is at 25 DEG C Thermal conductivity is 30W/mK, and silica is 1W/mK in 25 DEG C of thermal conductivity.

If including organic substance in adhesive layer 20, in high-power exciting lights such as illuminated laser light sources, It is possible that will produce discoloration in the organic substance for including in adhesive layer 20, burning and the decrease in transmission of light.Therefore, adhesive layer 20 preferably do not include organic substance as far as possible, but according to the power density of exciting light, it is organic can also to take the circumstances into consideration addition dispersant etc. Substance.

In addition, the adhesive layer 20 formed by nano-particle adhesion body can also be in inside as shown in Fig. 3 and aftermentioned Fig. 5 As include nanovoids (slight void) 27.Here, so-called nanovoids 27 refer to the aperture being formed in adhesive layer 20 Gap less than 0.3 μm.Thus, for example the gap for the part being formed in other than adhesive layer 20, the gap that aperture is 0.3 μm or more It is not included in nanovoids 27.In addition, so-called aperture refers in the feelings that the shape of nanovoids 27 is assumed to perfect sphere Diameter under condition.The aperture of nanovoids 27 is usually 5~15nm or so.

Fig. 7 is one of the chart of the pore-size distribution of the nanovoids 27 for the wavelength conversion body for indicating aftermentioned embodiment 1 Example.As shown in Figure 7, the average pore size of nanovoids 27 isThe left and right (10nm).

The shape of nanovoids 27 is not particularly limited, but generally spherical.(minor axis is the length-width ratio of nanovoids 27 It is long) it is usually 1：1~1：10.Nanovoids 27 are the remainings when nano-particle 21 carries out adhesion and forms nano-particle adhesion body Gap between nano-particle 21.

Nanovoids 27 make the ingredient for the light being enclosed in fluorophor particle 10 by making the refractive index of adhesive layer 20 reduce Increase, to show to improve the effect for the light extraction efficiency for carrying out auto-adhesive layer 20.Therefore, if including to receive in adhesive layer 20 Rice gap 27, it is likely that make output facula diameter narrowization, and improve the efficiency of output light, therefore preferably.

Therefore, nanovoids of the preferred adhesive layers 20 of wavelength conversion body 1A in the internal gap comprising aperture less than 0.3 μm 27。

Scanning electron microscope (SEM) photo or transmission electron microscope of the plane of disruption of wavelength conversion body 1A are shown (TEM) example of photo.Fig. 4 is the scanning electron microscope of the plane of disruption of the wavelength conversion body of aftermentioned embodiment 1 (SEM) example of photo.Fig. 5 is an example of transmission electron microscope (TEM) photo of the part B of Fig. 4.Fig. 6 It is scanning electron microscope (SEM) photo as the fluorophor particle of the raw material of the wavelength conversion body of aftermentioned embodiment 1 An example.

As shown in Figure 4, pass through the shape between the surface and fluorophor particle 10 of fluorophor particle (YAG particles) 10 At adhesive layer 20, adjacent fluorophor particle 10 is each other by 20 adhesion of adhesive layer, to form wavelength conversion body 1A.Adhesive layer 20 Nano-particle adhesion body made of 21 adhesion of nano-particle by multiple aluminium oxide is formed.

The SEM photograph that the fluorophor particle 10 of adhesive layer 20 will not formed is shown in Figure 6.As shown in Figure 6, For the fluorophor particle 10 for not forming adhesive layer 20, gap 15 is formed between adjacent fluorophor particle 10, it is adjacent Fluorophor particle 10 each other without adhesion.

As shown in Figure 4, in wavelength conversion body 1A, the surface of each fluorophor particle 10 shown in Fig. 6 The adhesive layer 20 formed by the nano-particle adhesion body of aluminium oxide is coating, and above-mentioned adhesive layer 20 is between fluorophor particle 10 Between.But not seamlessly filled by adhesive layer 20 between adjacent fluorophor particle 10, but in a part for adhesive layer 20 In be formed with gap 25.In addition, the wavelength conversion body other than present embodiment can also be made between adjacent fluorophor particle 10 Wavelength conversion body made of seamlessly being filled by adhesive layer 20 replaces wavelength conversion body 1 shown in Fig. 4.

Fig. 5 is an example of transmission electron microscope (TEM) photo of the part B of the adhesive layer 20 of Fig. 4.Fig. 5 is By the figure of the part B amplifying observations of Fig. 4.As shown in Figure 5, adhesive layer 20 is glued by the nano-particle 21 of multiple aluminium oxide Nano-particle adhesion body is formed made of even.In addition, as shown in Figure 5, it is viscous being formed by nano-particle adhesion body Close the nanovoids 27 that a diameter of 15nm, 5nm or so are formed in layer 20.These nanovoids 27 are presently considered to be in multiple nanometers 21 adhesion of particle and while forming the adhesive layer 20 formed by nano-particle adhesion body, remain in the gap between nano-particle 21.

The thickness of wavelength conversion body 1A is not particularly limited, such as is set as 40~400 μm, is preferably set to 80~200 μ m.If the thickness of wavelength conversion body 1A is in above range, thermal diffusivity can be maintained higher, therefore preferably.

(manufacturing method of wavelength conversion body)

Wavelength conversion body 1A can for example be manufactured by the following method.First, the molten of nano-particle 21 will be dispersed with Liquid mixes with fluorophor particle 10 and makes mixed liquor.In addition, in mixed liquor, it is added as needed on dispersant.Mixed liquor example Viscosity is adjusted such as in the way of as paste.The adjustment of viscosity is for example by adjusting nano-particle 21, fluorophor particle 10 The concentration of solid constituents is waited to carry out.

Then, the mixed liquor of the paste is applied on the substrates such as metal substrate 80.The coating of the mixed liquor of paste is for example Can be used that the coating for having used the applicator for having rod coater, silk-screen printing etc. carry out under atmospheric pressure environment is various well known Coating method.

In turn, make its solidification by keeping the mixed liquor of the paste on substrate 80 dry.Mixed liquor is solidified to form dry Dry body becomes following wavelength conversion body 1A, which has：Multiple fluorophor particles 10；With by multiple nano-particles 21 The adhesive layer 20 that nano-particle adhesion body made of adhesion forms and adjacent fluorophor particle 10 is made to stick to each other.

The drying of mixed liquor is for example by placing or being added at normal temperatures the substrate 80 for being coated with the mixed liquor of paste Heat carries out.Heating temperature in the case where being heated is, for example, 100 DEG C.

The nano-particle adhesion body made of 21 adhesion of multiple nano-particles of adhesive layer 20 is formed, can only by from comprising Water equal solvent is removed in the mixed liquor of nano-particle 21 to make, and nano-particle 21 need not be burnt into.So, originally The wavelength conversion body 1A of embodiment can be manufactured without heating at high temperature, therefore productivity is high, is in addition not easy to produce The deterioration of the raw fluorophor particle 10 caused by high-temperature heating.

The effect of wavelength conversion body 1A and wavelength converting member 100A are illustrated.The wavelength for constituting present embodiment turns The wavelength conversion body 1A for changing component 100A passes through illuminated exciting light so that the fluorophor particle 10 in wavelength conversion body 1A is swashed It sends out and radiates secondary light.In addition, being formed with the nanometer made of 21 adhesion of multiple nano-particles on the surface of fluorophor particle 10 The adhesive layer 20 that particle adhesion body is formed.But since the excitation transmitance of nano-particle 21 is high, make the effect ratio of light scattering Smaller (scattering basal area is small), therefore exciting light can expose to fluorophor particle 10, fluorophor particle through adhesive layer 20 10 are excited and radiate secondary light.

In the case where it is low substrate 80 of transmitance to constitute the substrate 80 of wavelength converting member 100A, in wavelength convert The secondary light that body 1A is generated is radiated from the surface side of wavelength conversion body 1A.In addition, in the base for constituting wavelength converting member 100A In the case that plate 80 is the high substrate 80 of transmitance, in the secondary light that wavelength conversion body 1A is generated from the table of wavelength conversion body 1A The surface side of surface side and substrate 80 is radiated.

It is resistance to constitute the nano-particle adhesion body of the composition adhesive layer 20 of the wavelength conversion body 1A of wavelength converting member 100A Nano-particle adhesion body made of the multiple adhesions of nano-particle of hot and high thermal diffusivity inorganic material.Therefore, the 1st embodiment party Even the wavelength conversion body 1A and wavelength converting member 100A of formula are using the high-power exciting light conduct such as laser light source Heat resistance and thermal diffusivity are also high in the case of exciting light.So, since the thermal diffusivity of adhesive layer 20 height, the 1st is implemented Even the wavelength conversion body 1A and wavelength converting member 100A of mode are using the high-power exciting light work such as laser light source In the case of for exciting light, it is not easy to produce the temperature quenching caused by the high temperature of fluorophor particle 10.

In addition, the wavelength conversion body 1A and wavelength converting member 100A of the 1st embodiment make to glue by nanovoids 27 Closing the refractive index of layer 20 reduces.Therefore, it according to the wavelength conversion body 1A and wavelength converting member 100A of the 1st embodiment, is easy Show the ingredient for the light being enclosed in fluorophor particle 10 increase and raising come auto-adhesive layer 20 light extraction efficiency effect Fruit is easy to make output facula diameter narrowization.Reflection of the effect in the visible light of the interface of wavelength conversion body 1A and substrate It is particularly significant in the case that component amount is bigger.So, the wavelength conversion body 1A and wavelength converting member of the 1st embodiment The optical characteristics of 100A is excellent.

In addition, organic matter quality included in adhesive layer 20 due to wavelength conversion body 1A is impurity levels at most It measures and few, even therefore in the case where having used the high-power exciting lights such as laser light source, being not easy to produce based on organic The discoloration of adhesive layer 20 caused by the heat deterioration of substance, adhesive layer 20 are burnt.Therefore, the wavelength convert of the 1st embodiment The heat resistance of body 1A and wavelength converting member 100A are high.

In turn, the adhesive layer 20 of wavelength conversion body 1A nano-particle adhesion bodily form made of multiple nano-particle adhesions At nano-particle 21 need not be burnt into.So, the wavelength conversion body 1A and wavelength convert structure of the 1st embodiment For part 100A due to that can form adhesive layer 20 without firing at high temperature, productivity is high.

In addition, the wavelength conversion body 1A and wavelength converting member 100A of the 1st embodiment are due to can be without in high temperature Under sintering form adhesive layer 20, therefore the fluorophor that heat resistance can be used low is as fluorophor particle 10.For example, (Sr, Ca)AlSiN₃：Although Eu fluorophor color renderings are excellent, oxidation reaction will produce under high temperature environment, therefore just have For the previous wavelength conversion body and wavelength converting member for the adhesive layer being sintered under high temperature, it is easy to generate oxidation in fluorophor It reacts and color rendering reduction.In contrast, for the wavelength conversion body 1A of the 1st embodiment and wavelength converting member 100A, Due to that can form adhesive layer 20 without sintering at high temperature, such fluorophor can also be used as fluorophor grain Son 10 uses, and color rendering can be made to improve.

It should be noted that for the wavelength conversion body 1A of the 1st embodiment, show to constituting receiving for adhesive layer 20 Rice corpuscles 21 and fluorophor particle 10 do not carry out the scheme being surface-treated etc..But the wavelength other than the 1st embodiment is turned It changes for body, it, can also be to the nano-particle 21 and fluorescence of composition adhesive layer 20 as long as not hindering the thermal diffusivity of wavelength conversion body At least either in body particle 10 is surface-treated.For should being surface-treated, such as in order to improve composition by nanoparticle 21 mutual adaptation of nano-particle, the compactness of nano-particle adhesion body of the adhesive layer 20 that sub- adhesion body is formed and in nanometer The surface of particle 21 carries out.In addition, for above-mentioned surface treatment, for example, in order to improve adhesive layer 20 and fluorophor particle 10 it Between adaptation, the compactness of wavelength conversion body and the surface of at least one of nano-particle 21 and fluorophor particle 10 into Row.

It in this case, can be suitable for use in the case where the power of exciting light is weaker.

[the 2nd embodiment]

The wavelength conversion body and wavelength converting member of 2nd embodiment are illustrated.Fig. 8 is the wave of the 2nd embodiment The schematic cross-sectional view of long conversion body and wavelength converting member comprising the wavelength conversion body.As shown in Figure 8, wavelength The wavelength conversion body 1B that translation building block 100B has substrate 80 and is formed on the substrate 80.

Wavelength converting member 100B be in fig. 2 shown in the 1st embodiment wavelength converting member 100A in use Wavelength conversion body 1B replaces the wavelength converting member of wavelength conversion body 1A.In addition, wavelength conversion body 1B and shown in Fig. 2 the The wavelength conversion body 1A of 1 embodiment is compared, and does not include emptying aperture in adhesive in a part for fluorophor particle encircled area 40 45 and on this point of including solid part 44, is different, other aspects are identical.

Therefore, wavelength conversion body 1B and wavelength converting member 100B as shown in fig. 8 are implemented with the shown in Fig. 2 1st In the wavelength conversion body 1A and wavelength converting member 100A of mode, the same symbol is marked to identical composition, by what is constituted and act on Explanation is omitted or simplified.

As shown in Figure 8, in the fluorophor particle encircled area 40 of wavelength conversion body 1B, fluorophor particle Encircled area 40Ba and 40Bd include emptying aperture 45 in adhesive, and fluorophor particle encircled area 40Bb and 40Bc include solid part 44.Here, so-called solid part 44 refers to not including emptying aperture in adhesive in the part in fluorophor particle encircled area 40 45 and the substantial part that is only formed by the nano-particle adhesion body for constituting adhesive layer 20.In addition, solid part 44 can also have Small gap, that is, the underbead crack 46 of emptying aperture 45 in volume ratio adhesive.

That is, in wavelength conversion body 1B as shown in fig. 8, by via adhesive layer 20 and the fluorophor particle 10 of adhesion is enclosed At at least part of fluorophor particle encircled area 40 to become not including the aperture in adhesive layer 20 be 0.3 μm or more of sky Emptying aperture 45 in gap, that is, adhesive.

As described above, emptying aperture 45 impacts the scattering of the visible light in wavelength conversion body 1B in adhesive.For example, If emptying aperture 45 is less in adhesive layer 20 in the adhesive that the aperture for easy ting produce the scattering of visible light is 0.3 μm~20 μm, Then the scattering of the visible light in wavelength conversion body 1B tails off.In this case, the waveguide ingredient in wavelength conversion body 1B becomes to hold It easily reduces, has the effect of improving light extraction efficiency, makes output facula diameter narrowization, therefore preferably.

Wavelength is passed through by the preferred effect of the few caused wavelength conversion body 1B of the content of emptying aperture 45 in above-mentioned adhesive Conversion body 1B is showed comprising emptying aperture in adhesive 45 at a specific ratio.Content by emptying aperture 45 in above-mentioned adhesive is few The preferred effect of caused wavelength conversion body 1B for example includes with 39 volume % ratios below by wavelength conversion body 1B Emptying aperture 45 in adhesive and show.

Fig. 9 is in the case of being broken the line B-B of wavelength conversion body 1B approximately along Fig. 8 of the 2nd embodiment One example of scanning electron microscope (SEM) photo of the plane of disruption.As shown in Figure 9, in wavelength conversion body 1B Fluorophor particle encircled area 40 the plane of disruption in be formed with the solid part 44 not comprising emptying aperture in adhesive 45.That is, in Fig. 9 Shown in the plane of disruption, the fluorophor particle encircled area 40 of wavelength conversion body 1B becomes high interstitital texture.

As shown in Figure 9, solid part 44 has gap, that is, underbead crack 46 of channel-shaped.Here, so-called inside is split Line 46 refers to the gap that the length formed in adhesive layer 20 is 10 μm or more, groove width is 2 μm of channel-shaped below.Underbead crack 46 Length, as groove width can also for example confirm in fig.9, can be confirmed by the micro- sem observation of the plane of disruption. The length-width ratio (minor axis is length) of underbead crack 46 is usually more than 1：10 and be 1：1000 or less.In addition, underbead crack 46 and bonding Emptying aperture 45 can be differentiated due to the numberical range difference of length-width ratio (minor axis is length) in agent.

Underbead crack 46 be not intended that figure at, it is believed that：Typically in the manufacture of wavelength conversion body 1B, due to making Thermal expansion, the contraction of above-mentioned raw materials when the raw material heat drying of wavelength conversion body 1B and generate.Therefore, it is believed that：Wavelength Conversion body 1B can inhibit the generation of the underbead crack 46 in solid part 44 by optimizing manufacturing condition, it is believed that pass through inhibition The generation of the underbead crack 46, to which film strength can be improved.

As will be described later, it is believed that：If underbead crack 46 is in view of its form and dimension, there are frequencies, will not be right Wavelength conversion body 1B and wavelength converting member 100B causes to offset the bad of the such degree of optical effect obtained by the present invention It influences.Therefore, underbead crack 46 is clearly distinguished with emptying aperture 45 in the adhesive of the present invention.

The effect display of wavelength conversion body 1B and wavelength converting member 100B and the wavelength conversion body 1A of the 1st embodiment and Wavelength converting member 100A is similarly acted on.

In addition, at least part that wavelength conversion body 1B becomes fluorophor particle encircled area 40 does not include sky in adhesive Hole 45.Therefore, the wavelength conversion body 1A and wavelength convert of wavelength conversion body 1B and wavelength converting member 100B and the 1st embodiment Component 100A is compared, and has the function of making the waveguide ingredient of the exciting light of wavelength conversion body 1B to be further reduced.

In addition, it is believed that：If underbead crack 46 is in view of its form and dimension, the effect of scatter visible light is small, transmission/ The effect for reflecting visible light is big.Therefore, it is believed that：Even if, will not be to wavelength conversion body 1B and wavelength there are underbead crack 46 Translation building block 100B causes to offset the harmful effect of the such degree of optical effect obtained by the present invention.

The effect of wavelength conversion body 1B and wavelength converting member 100B play with the wavelength conversion body 1A of the 1st embodiment and The same effects of wavelength converting member 100A.

In addition, wavelength conversion body 1B and wavelength converting member 100B become at least one of fluorophor particle encircled area 40 Divide and does not include emptying aperture 45 in adhesive.Therefore, according to wavelength conversion body 1B and wavelength converting member 100B, then with the 1st embodiment party The wavelength conversion body 1A and wavelength converting member 100A of formula are compared, and can further be played and be improved adhesive layer 20 and coefficient of thermal expansion ratio The effect of the adaptation of higher substrate 80.

In addition, at least part due to fluorophor particle encircled area 40 does not include emptying aperture 45 in adhesive, wave Long conversion body 1B and wavelength converting member 100B can be played further compared with wavelength conversion body 1A and wavelength converting member 100A The effect of waveguide ingredient reduction.Therefore, according to wavelength conversion body 1B and wavelength converting member 100B, then with the 1st embodiment Wavelength conversion body 1A and wavelength converting member 100A are compared, and are easy to improve light extraction efficiency, are made output facula diameter narrowization, because This is with more excellent optical characteristics.

[the 3rd embodiment]

The wavelength conversion body and wavelength converting member of 3rd embodiment are illustrated.Figure 10 is the wave of the 3rd embodiment The schematic cross-sectional view of long conversion body and wavelength converting member comprising the wavelength conversion body.As shown in Figure 10, wave The wavelength conversion body 1C that long translation building block 100C has substrate 80 and formed on the substrate 80.

Wavelength converting member 100C be in fig. 2 shown in the 1st embodiment wavelength converting member 100A in use Wavelength conversion body 1C replaces the wavelength converting member of wavelength conversion body 1A.In addition, wavelength conversion body 1C and shown in Fig. 2 the The wavelength conversion body 1A of 1 embodiment is compared, and is different on this point adhesive layer 20 further includes high radiating part 50, His aspect is identical.

Therefore, wavelength conversion body 1C and wavelength converting member 100C as shown in fig. 10 are implemented with the shown in Fig. 2 1st In the wavelength conversion body 1A and wavelength converting member 100A of mode, the same symbol is marked to identical composition, by what is constituted and act on Explanation is omitted or simplified.

As shown in Figure 10, in wavelength conversion body 1C, high dissipate is further included between adjacent adhesive layer 20 Hot portion 50.Here, so-called high radiating part 50 refers to being formed by the material higher than nano-particle 21 of the thermal conductivity at 25 DEG C and grain The part that diameter is 1 μm or more.If adhesive layer 20 is including formed by the material higher than nano-particle 21 of the thermal conductivity at 25 DEG C High radiating part 50, then the thermal diffusivity of wavelength conversion body 1C and wavelength converting member 100C get higher, can inhibit to be drawn by temperature quenching The efficiency risen reduces.

High radiating part 50 is usually 10W/mK or more in 25 DEG C of thermal conductivity, preferably 35W/mK or more, more preferably For 50W/mK or more.If high radiating part 50 25 DEG C thermal conductivity within the above range, wavelength conversion body 1C and wavelength The thermal diffusivity of translation building block 100C can fully be got higher, and can effectively inhibit the efficiency caused by temperature quenching reduces.In addition, In the case that high radiating part 50 has the anisotropy of thermal conductivity, if the highest direction of thermal conductivity in high radiating part 50 Thermal conductivity within the above range, then the thermal diffusivity of wavelength conversion body 1C and wavelength converting member 100C can fully be got higher, therefore It is preferred that.

The shape of high radiating part 50 is not particularly limited, such as granular, flakey can be made etc..In fluorophor particle 10 Including in the case of the fluorophor particle 10 of the shape with the garnet structure for being derived from fluorophor particle 10, if high heat dissipation The shape in portion 50 is flakey, then can improve the particle-filled density of wavelength conversion body 1C, therefore preferably.

As shown in Figure 10, high radiating part 50 is included between adjacent adhesive layer 20.That is, the table of high radiating part 50 Face becomes not contact with fluorophor particle 10, and is contacted with adhesive layer 20.Like this, if high radiating part 50 is glimmering between one Adhesive layer 20 that the surface of body of light particle 10 is formed and between the adhesive layer 20 that the surface of another fluorophor particle 10 is formed, Then the heat transfer between adhesive layer 20 improves, therefore preferably.

As the material of high radiating part 50, such as boron nitride, aluminium oxide can be used etc..Wherein, heat of the boron nitride at 25 DEG C Conductance is high, therefore preferably.

Figure 11 is that the wavelength conversion body of the 3rd embodiment as shown in fig. 10 and the wavelength comprising the wavelength conversion body turn Change an example of scanning electron microscope (SEM) photo of the plane of disruption comprising high radiating part 50 in component.Such as Figure 11 Shown in like that, the adhesive layer 20 that high radiating part 50 is formed between the surface of fluorophor particle 10 with it is glimmering at another Between the adhesive layer 20 that the surface of body of light particle 10 is formed.

The effect display of wavelength conversion body 1C and wavelength converting member 100C and the wavelength conversion body 1A of the 1st embodiment and Wavelength converting member 100A is similarly acted on.

In addition, wavelength conversion body 1C includes the high heat dissipation formed by the material higher than nano-particle 21 of the thermal conductivity at 25 DEG C Portion 50.Therefore, the wavelength conversion body 1A and wavelength convert of wavelength conversion body 1C and wavelength converting member 100C and the 1st embodiment Component 100A is compared, thermal diffusivity higher, and can further suppress the efficiency caused by temperature quenching reduces.

The effect of wavelength conversion body 1C and wavelength converting member 100C play with the wavelength conversion body 1A of the 1st embodiment and The same effects of wavelength converting member 100A.

In addition, wavelength conversion body 1C and wavelength converting member 100C between adjacent adhesive layer 20 due to further including height Radiating part 50, thus compared with the wavelength conversion body 1A of the 1st embodiment and wavelength converting member 100A, thermal diffusivity higher, energy Enough further suppressing the efficiency caused by temperature quenching reduces.

[the 4th embodiment]

The wavelength conversion body and wavelength converting member of 4th embodiment are illustrated.Figure 12 is the wave of the 4th embodiment The skeleton diagram of the section of long conversion body and wavelength converting member comprising the wavelength conversion body.

As shown in fig. 12, wavelength converting member 100D (100) has substrate 80 and is formed on the substrate 80 Wavelength conversion body 1D (1).A wavelength conversion body 1D is arranged in wavelength converting member 100D on the surface of a substrate 80.Such as A wavelength conversion body 1D is arranged in fruit on the surface of a substrate 80, then the manufacture of wavelength converting member 100D is easy.

The wavelength converting member 100D (100) of 4th embodiment is in the wavelength converting member 100A of the 1st embodiment Wavelength conversion body 1A is substituted for wavelength converting member obtained from wavelength conversion body 1D.80 use of substrate and the 1st embodiment The same substrates of wavelength converting member 100A.

As shown in fig. 12, the wavelength conversion body 1D (1) of the 4th embodiment and the wavelength of the 1st embodiment turn Change body 1A similarly has planar exit facet 2 with the surface of 80 opposite side of substrate.But wavelength conversion body 1D (1) and the 1st The wavelength conversion body 1A of embodiment is different, and planar exit facet 2 has male and fomale(M＆F) 3 and flat surface 4.Here, so-called flat surface 4 Refer to the concave-convex face fewer than male and fomale(M＆F) 3, refers to specifically the face for meeting Ra≤0.15 μm and Rz≤0.3 μm.That is, planar At least part of exit facet 2 becomes the flat surface 4 for meeting Ra≤0.15 μm and Rz≤0.3 μm.In addition, in fig. 12, being Convenient for explanation, male and fomale(M＆F) 3 more emphatically indicated than reality.

Figure 13 is the schematic of the wavelength conversion body of the 4th embodiment and the wavelength converting member comprising the wavelength conversion body Cross-section diagram.Figure 13 is the figure for indicating the section of wavelength conversion body 1D (1) shown in Figure 12 in more detail.

As shown in Figure 12 and 13, wavelength conversion body 1D in fig. 2 shown in the 1st embodiment wavelength convert In body 1D, planar exit facet 2 has male and fomale(M＆F) 3 and flat surface 4.As flat surface 4 is as shown in Figure 13, such as pass through shape Become flat at at least part on the surface of the adhesive layer 20 of planar exit facet 2 and obtains.

The nano-particle adhesion body 23 made of 21 adhesion of multiple nano-particles of adhesive layer 20 is formed.The adhesive layer 20 is for example It is obtained by operations described below：In the manufacture of wavelength conversion body 1D, the nano-particle 21 being filled between fluorophor particle 10 is logical Heat drying processing etc. is crossed to carry out adhesion and form nano-particle adhesion body 23.Therefore, with regard to flat surface shown in Figure 13 4 and Speech, such as make the side for becoming flat surface according to the interface of substrate 80 and adhesive layer 20 using the high nano-particle 21 of mobility Formula carry out it is closely sealed made of wavelength conversion body, shape in the release surface in the case where removing the wavelength conversion body from substrate 80 At.In addition, if the table back side of the wavelength conversion body of stripping overturn, and become new plane according to the surface comprising release surface Wavelength conversion body and the adhesion again of substrate 80 can then be obtained having with flat comprising flat surface 4 by the mode of shape exit facet 2 The wavelength converting member 100D of the wavelength conversion body 1D of planar exit facet 2.

Flat surface 4 is preferably 36% or more relative to the occupation rate of the area of planar exit facet 2, and more preferably 65.5% More than.If the occupation rate of flat surface 4 is within the above range, it is easy to improve the absorption efficiency of exciting light.Therefore, flat surface 4 Occupation rate wavelength conversion body 1D within the above range and have the wavelength converting member 100D of wavelength conversion body 1D for The purposes of projector etc. is useful.

In addition, the wavelength conversion body 1D of the 4th embodiment can also carry out AR coatings on the surface of 2 side of planar exit facet Deng well known antireflection coating processing.If the surface in 2 side of planar exit facet of wavelength conversion body 1D carries out antireflection painting Processing is applied, then is easy to improve the absorption efficiency and light extraction efficiency of exciting light.

In turn, although it is not shown, but the wavelength conversion body 1D of the 4th embodiment can also be in 2 side of planar exit facet Surface forms the face crack in the gap as channel-shaped.Here, so-called face crack is that such as width is for 10 μm or more and deep The slot that degree is 1 μm or more.

In addition, for the wavelength conversion body 1B of the 2nd embodiment, underbead crack 46 is formed in the interior of wavelength conversion body 1B The solid part 44 in portion.In contrast, for the wavelength conversion body 1D of the 4th embodiment, face crack be formed in it is planar go out Penetrate the surface of 2 side of face.So, face crack can be differentiated from underbead crack 46 since the position of formation is different.

The face crack of 4th embodiment be not intended that figure at, it is believed that：The inside of itself and the 2nd embodiment is split Line 46 similarly, typically in the manufacture of wavelength conversion body 1D, when raw material heat drying due to making wavelength conversion body 1D Thermal expansion, the contraction of above-mentioned raw materials and generate.Therefore, it is believed that：Wavelength conversion body 1D can by optimize manufacturing condition come Inhibit the generation of face crack.

In addition, it is believed that：If face crack is in view of its shape, size and spacing etc., there are frequencies, scatter visible The effect of light is small, and the effect of transmission/reflection/angle visible light is big.Therefore, it is believed that：Even if, will not be to wavelength there are face crack Conversion body 1D and wavelength converting member 100D causes to offset the harmful effect of the such degree of optical effect obtained by the present invention.

Figure 14 is scanning electron microscope (SEM) photo for the planar exit facet 2 for indicating section shown in Figure 13 An example.As shown in Figure 14, flat surface 4 is formed in the planar exit facet 2 of wavelength conversion body 1D.

The effect display of wavelength conversion body 1D and wavelength converting member 100D and the wavelength conversion body 1A of the 1st embodiment and Wavelength converting member 100A is similarly acted on.

In addition, wavelength conversion body 1D and wavelength converting member 100D due to planar exit facet 2 have flat surface 4, It is easy to improve the absorption efficiency of exciting light.

The effect of wavelength conversion body 1D and wavelength converting member 100D play with the wavelength conversion body 1A of the 1st embodiment and The same effects of wavelength converting member 100A.

In addition, wavelength conversion body 1D and wavelength converting member 100D due to planar exit facet 2 have flat surface 4, It is easy to improve the absorption efficiency of exciting light.Therefore, has the wavelength converting member 100D of wavelength conversion body 1D for projector etc. Purposes be useful.

[variation]

As the variation of wavelength conversion body, can use by the wavelength conversion body 1A of above-mentioned 1st~the 4th embodiment, The wavelength conversion body for the structure that the respective feature of 1B, 1C and 1D is composed.Effect/effect of the variation becomes based on each The combination of effect/effect of the feature of wavelength conversion body.

In addition, the variation as wavelength converting member, can use and turn the wavelength of above-mentioned 1st~the 4th embodiment Change the wavelength converting member for the structure that the respective feature of component 100A, 100B, 100C and 100D is composed.The work of the variation Become the combination of effect/effect of the feature based on each wavelength converting member with/effect.

For the wavelength converting member 100 (100A, 100B, 100C and 100D) of above-mentioned 1st~the 4th embodiment, show The example of a wavelength conversion body 1 (1A, 1B, 1C and 1D) is gone out to be arranged on the surface of a substrate 80.But as wavelength The variation of translation building block 100 can use and be provided with more than two wavelength conversion bodies 1 on the surface of a substrate 80 and form Structure wavelength converting member.According to the variation, it is special that multiple wavelength converts can be formed on the surface of a substrate 80 The different wavelength conversion body 1 of property.

[light-emitting device]

If using the wavelength conversion body or wavelength converting member of above-mentioned 1st~the 4th embodiment and to wavelength conversion body The excitaton source of the suitable exciting light of irradiation can then obtain the light-emitting device for obtaining white light.As excitaton source, can use known Excitaton source.

Embodiment

Hereinafter, present embodiment is described in more detail by embodiment, but present embodiment is not limited to these Embodiment.

[embodiment 1]

(preparation of mixed solution)

First, as fluorophor particle, prepare average grain diameter D₅₀YAG particles (the Nemoto Lumi- for being about 20.5 μm Materials Company Limited YAG462E205).In addition, as nano-particle, preparation is dispersed with average grain diameter D₅₀ It is aqueous solution made of the nano-particle of the aluminium oxide of about 20nm (CIK NanoTek Corporation ALW10WT-G0). Then, above-mentioned YAG particles are added in the above-mentioned aqueous solution for being dispersed with nano-particle, mix and are rubbed, it is mixed to have made nano-particle Close solution (nano-particle mixed solution No.1).

(coating of nano-particle mixed solution)

Adhesive tape is attached on metal substrate made of aluminum and forms step difference, is added dropwise by step difference portion enclosed Nano-particle mixed solution is coated with nano-particle mixed solution No.1 using the applicator for having rod coater.

(formation of wavelength conversion body)

The metal substrate for being coated with nano-particle mixed solution No.1 is dried at normal temperatures, as a result on metallic substrates The hirudo leech that film thickness is 100 μm are arrived.The hirudo leech become with YAG particles and by multiple aluminium oxide nano-particle adhesion Made of nano-particle adhesion body formed and by adjacent YAG particles each other with the wave of the adhesive layer of nano-particle adhesion body adhesion Long conversion body (wavelength conversion body No.1).It has obtained being formed with the membranaceous wavelength that thickness is 100 μm on metallic substrates as a result, The wavelength converting member (wavelength converting member No.1) of conversion body No.1.

(evaluation)

<Micro- sem observation>

By the plane of disruption of wavelength conversion body No.1 scanning electron microscope (SEM) and transmission electron microscope (TEM) it is observed.Fig. 4 is that the scanning electron microscope (SEM) of the plane of disruption of the wavelength conversion body No.1 of embodiment 1 shines One example of piece.Fig. 5 is an example of transmission electron microscope (TEM) photo of the part B of Fig. 4.Fig. 6 is as reality Apply an example of scanning electron microscope (SEM) photo of the fluorophor particle of the raw material of the wavelength conversion body No.1 of example 1.

As shown in Figure 4, by being formed between the surface and YAG particles 10 of YAG particles (fluorophor particle) 10 Adhesive layer 20, adjacent YAG particles 10 are each other by 20 adhesion of adhesive layer, so as to form 1 (wavelength conversion body of wavelength conversion body No.1).Nano-particle adhesion body made of nano-particle adhesion of the adhesive layer 20 by multiple aluminium oxide is formed.

The SEM photograph that the YAG particles 10 of adhesive layer 20 will not formed is shown in Figure 6.Fig. 6 be in order to be dispersed with nanometer The aqueous solution of particle is mixed and the YAG particles that use.As shown in Figure 6, the YAG of adhesive layer 20 is not just formed For particle 10, gap 15 is formed between adjacent YAG particles 10, adjacent YAG particles 10 are each other without adhesion.

As shown in Figure 4, each shown in Fig. 6 for wavelength conversion body 1 (wavelength conversion body No.1) The adhesive layer 20 that the surface of YAG particles 10 is formed by the nano-particle adhesion body of aluminium oxide is coating, and above-mentioned adhesive layer 20 Between YAG particles 10.But not seamlessly filled by adhesive layer 20 between adjacent YAG particles 10, but in adhesive layer Gap 25 is formed in 20 part.

Fig. 5 is an example of transmission electron microscope (TEM) photo of the part B of the adhesive layer 20 of Fig. 4.Fig. 5 is By the figure of the part B amplifying observations of Fig. 4.As shown in Figure 5, adhesive layer 20 is glued by the nano-particle 21 of multiple aluminium oxide Nano-particle adhesion body is formed made of even.In addition, as shown in Figure 5：In the adhesive layer 20 formed by nano-particle adhesion body It is formed with the nanovoids 27 of a diameter of 15nm, 5nm or so.It is believed that：These nanovoids 27 are in multiple nano-particles 21 The gap between nano-particle 21 is remained in when carrying out adhesion and forming the adhesive layer 20 formed by nano-particle adhesion body.

Determine the aperture of the nanovoids 27 of wavelength conversion body No.1.The aperture of nanovoids 27 be by using The nitrogen adsorption method of the Autosorb (registered trademark) -3 of Quantachrome Corporation measures.It shows the result in In Fig. 7.As shown in Figure 7：It is there are apertures for the inside of wavelength conversion body No.1The nanovoids 27 of the left and right (10nm).

Wavelength converting member No.1 is attached on metal radiator.Then, it is determined from wave by thermoviewer The temperature on the surface of the wavelength conversion body when surface side irradiation central wavelength lambda of long conversion body No.1 is the laser of 450nm.Laser The power setting of light source is 3.5W, and the incident angle of laser is set as 45 °, and the irradiation time of laser is set as 60 seconds.In table 1 The measurement result of the temperature on the surface of wavelength conversion body is shown.

[table 1]

[embodiment 2]

Instead of nano-particle mixed solution No.1, the nano-particle solid component concentration using aluminium oxide is embodiment 1 1.3 times of the nano-particle mixed solution (nano-particle mixed solution No.2) of nano-particle mixed solution, in addition to this with reality It applies example 1 equally to be operated, has obtained wavelength converting member (wavelength converting member No.2).

[embodiment 3]

In the nano-particle mixed solution No.1 obtained in embodiment 1,5 matter are added relative to 100 mass parts of YAG particles Measure the average grain diameter D of part₅₀It is about 10 μm of boron nitride particles (Showa Denko K. K SHOBN), mix and rub, obtain Nano-particle mixed solution No.3.Instead of nano-particle mixed solution No.1, nano-particle mixed solution No.3 has been used, has removed this It is equally operated with embodiment 1 in addition, has obtained wavelength converting member (wavelength converting member No.3).

[embodiment 4]

Apply bending stress by the metal substrate tool of the wavelength converting member NO.1 to being obtained in embodiment 1, from And metal substrate is made intentionally to be removed with wavelength conversion body No.1.The table back side of the wavelength conversion body No.1 of stripping is overturn, By wavelength conversion body No.1 in the way of the new surface (planar exit facet) that release surface becomes with metal substrate opposite side With metal substrate adhesion again.Wavelength converting member (the wavelength of metal substrate and wavelength conversion body No.4 is obtained including as a result, Translation building block No.4).

The surface shape of wavelength conversion body No.4 is analyzed to obtained wavelength converting member No.4.

The surface of wavelength conversion body No.4 is determined 10 times by contact pin type step meter (Bruker corporation DEKTAK) The scanning distance of 2mm.It is aware of as a result,：On the surface of wavelength conversion body 4, there are the flat of Ra≤0.15 μm and Rz≤0.3 μm This 2 regions of the recess portion that smooth face and groove width are 10mm or more and depth is 1mm or more.In addition, Ra is to implement 10 2mm to sweep Retouch, be set as the average value of the measured value of 10 secondary amounts of ratio in 1 axis data shared by flat surface.

[comparative example 1]

Instead of nano-particle mixed solution, organic siliconresin (Shin-Etsu Chemial Co., Ltd two-component RTV has been used Silicon rubber KE106), it is equally operated with embodiment 1 in addition to this, has obtained being formed with thickness on metallic substrates being 100 μ The wavelength converting member of the membranaceous wavelength conversion body of m.The wavelength conversion body of the wavelength converting member become have YAG particles and The wavelength convert structure of adhesive layer made of being formed by organic siliconresin and being bonded adjacent YAG particles with organic siliconresin each other Part.

Using obtained wavelength conversion body, laser irradiation experiment has been carried out similarly to Example 1.It needs to illustrate It is that in laser irradiation experiment, adhesive layer is burnt during experiment.It shows the result in table 1.As shown in Table 1： For the wavelength conversion body of embodiment 1 compared with the wavelength conversion body of comparative example 1, thermal diffusivity and thermal diffusivity are high.

[embodiment 5]<The wavelength conversion body of the mixed liquor comprising ZnO sol gel solutions and ZnO nanoparticle is used Making>

(preparation of mixed liquor)

First, prepare average grain diameter D₅₀It is about 20 μm of YAG fluorophor powders.In addition, YAG fluorophor powders are to pass through biography The solid phase reaction of system and the fluorophor powder synthesized.In addition, by making 2 hydrate of zinc acetate be scattered in methanol, to obtain Include the sol gel solution of 10 mass % zinc acetates.Then, by YAG fluorophor powders 1.0g, sol gel solution 0.5g With the suspension 0.5g for being dispersed with the zinc oxide nano-particle that the average grain diameter of 30 mass % is 20nm be obtained by mixing Mixed liquor (mixed liquor No.5).

(making of inorganic wavelength conversion body)

The metal substrate polylith of the long 20mm made of aluminium alloy, horizontal 20mm, thickness 0.5mm are continuously arranged, in each gold Belong to and attach kapton adhesive tape (thickness 0.1mm) around substrate, step difference is set.In being enclosed by step difference for each metal substrate At part be added dropwise mixed liquor No.5 and made wavelength conversion body.Specifically, by step difference portion enclosed, use Applicator is existed after making solvent seasoning by hot plate with 100 DEG C, 1 hour using drying oven by rod coating coating mixture No.5 It is heated 5 hours at 350 DEG C.It has obtained being formed with inorganic wavelength conversion body (wavelength conversion body No.5) on metallic substrates as a result, Wavelength converting member (wavelength converting member No.5).The thickness of wavelength conversion body No.5 is identical as the thickness of kapton adhesive tape. The average grain diameter for constituting the nano-particle of the adhesive layer between connection fluorophor particle 10 is 10~20nm.

For constituting the wavelength conversion body No.5 of obtained wavelength converting member No.5, similarly to Example 1 with sweeping Retouch the plane of disruption that type electron microscope (SEM) observes wavelength conversion body No.5.It is observed in the plane of disruption of wavelength conversion body No.5 Such underbead crack 46 shown in a small amount of Fig. 9 is arrived.

[embodiment 6]<The making of the wavelength conversion body of the ZnO sol gel solutions not comprising nano-particle is used>

(preparation of mixed liquor)

First, prepare average grain diameter D₅₀It is about 20 μm of YAG fluorophor powders.In addition, YAG fluorophor powders are to pass through biography The solid phase reaction of system and the powder synthesized.In addition, it includes 10 matter to have been obtained by so that 2 hydrate of zinc acetate is scattered in methanol Measure the sol gel solution of the zinc acetate of %.Then, by above-mentioned YAG fluorophor powders 1.0g and above-mentioned sol gel solution 0.5g It carries out being obtained by mixing mixed liquor (mixed liquor No.6).

(making of inorganic wavelength conversion body)

The metal substrate polylith of the long 20mm made of aluminium alloy, horizontal 20mm, thickness 0.5mm are continuously arranged, in each gold Belong to and attach kapton adhesive tape (thickness 0.1mm) around substrate, is provided with step difference.In each metal substrate by step difference institute The part surrounded is added dropwise mixed liquor No.6 and has made wavelength conversion body.Specifically, making by step difference portion enclosed Existed using drying oven after making solvent seasoning by hot plate with 100 DEG C, 1 hour by rod coating coating mixture No.6 with applicator It heated at 350 DEG C 5 hours.It has obtained being formed with inorganic wavelength conversion body (wavelength conversion body on metallic substrates as a result, No.6 wavelength converting member (wavelength converting member No.6)).The thickness of the thickness and kapton adhesive tape of wavelength conversion body No.6 It is identical.The average grain diameter for constituting the nano-particle of the adhesive layer between connection fluorophor particle 10 is less than 10nm.

For constituting the wavelength conversion body No.6 of obtained wavelength converting member No.6, similarly to Example 1 with sweeping Retouch the plane of disruption that type electron microscope (SEM) observes wavelength conversion body No.6.It is observed in the plane of disruption of wavelength conversion body No.6 To such underbead crack 46 shown in a large amount of Fig. 9.

(comparison of embodiment 5 and embodiment 6)

It is observed from SEM：The wavelength conversion body No.5 of embodiment 5 is interior compared with the wavelength conversion body No.6 of embodiment 6 The yield of portion's crackle is few.In addition, for the grain size of the nano-particle of the adhesive layer between constituting connection fluorophor particle 10, it is real The wavelength conversion body No.6 for applying example 6 is smaller than the wavelength conversion body No.5 of embodiment 5.Therefore, it is believed that：If constituting connection fluorescence The size of the particle of adhesive layer between body particle 10 is too small, then will produce more underbead crack.

It is believed that：Underbead crack be due to by as raw material mixed liquor make wavelength conversion body when drying, firing when Generated internal stress and generate.Therefore, it is believed that：If the grain size for constituting the nano-particle of adhesive layer is too small, glimmering Pore volume between body of light particle 10 reduces, and underbead crack increases.

It is aware of：As described above, it is set by the way that the grain size of the nano-particle of the adhesive layer between keeping fluorophor will be constituted For average grain diameter 10nm or more so that the generation of underbead crack is inhibited.

No. 2015-242020 (the applying date of Japanese Patent Application：On December 11st, 2015) full content have been incorporated.

More than, the content of present embodiment is illustrated according to embodiment, but present embodiment is not limited to these It records, it is self-evident to those skilled in the art that can carry out various modifications and improvement.

Industrial availability

Even wavelength conversion body, wavelength converting member and the light-emitting device of the present invention are in illuminated high-power excitation Heat resistance and thermal diffusivity are also excellent in the case of light, and productivity is excellent.

The explanation of symbol

1,1A, 1B, 1C, 1D wavelength conversion body

2 planar exit facets

3 male and fomale(M＆F)s

4 flat surfaces

10 fluorophor particles (YAG particles)

15 gaps

20 adhesive layers

21 nano-particles

23 nano-particle adhesion bodies

25 gaps

27 nanovoids (slight void)

The coating fluorophor particle of 30 nano-particles

40 fluorophor particle encircled area

44 solid parts

Emptying aperture in 45 adhesives

46 crackles

50 high radiating parts

80 substrates

100,100A, 100B, 100C, 100D wavelength converting member

Claims

1. a kind of wavelength conversion body, which is characterized in that have：

Multiple fluorophor particles；With

Adhesive layer, the adhesive layer is by multiple average grain diameter D₅₀It is received made of nano-particle adhesion for 1nm less than 100nm Rice corpuscles adhesion body forms and the adjacent fluorophor particle is made to stick to each other.

2. wavelength conversion body according to claim 1, which is characterized in that the average grain diameter D of the nano-particle₅₀For 10nm Less than 100nm.

3. wavelength conversion body according to claim 1 or 2, which is characterized in that the fluorophor particle includes following fluorescence Body particle：By after the firing of 1200 DEG C or more of fluorophor particle in an atmosphere brightness divided by 1200 DEG C or more in an atmosphere Brightness maintenance rate obtained from brightness before the firing of fluorophor particle is 80% or less.

4. wavelength conversion body described in any one of claim 1 to 3, which is characterized in that the adhesive layer is wrapped in inside Nanovoids containing the gap as aperture less than 0.3 μm.

5. wavelength conversion body according to any one of claims 1 to 4, which is characterized in that by via the adhesive layer and At least part for the fluorophor particle encircled area that the fluorophor particle of adhesion is surrounded does not include in the adhesive layer Aperture be emptying aperture in 0.3 μm or more of gap, that is, adhesive.

6. wavelength conversion body according to any one of claims 1 to 5, which is characterized in that with 39 volume % ratios below Example includes emptying aperture in described adhesive.

7. according to wavelength conversion body according to any one of claims 1 to 6, which is characterized in that in the adjacent adhesive layer Between, it further includes and is formed by the material higher than the nano-particle of the thermal conductivity at 25 DEG C and grain size is 1 μm or more high Radiating part.

8. wavelength conversion body according to claim 7, which is characterized in that the high radiating part is in 25 DEG C of thermal conductivity 10W/mK or more.

9. wavelength conversion body according to claim 7 or 8, which is characterized in that the high radiating part is between described in one Adhesive layer that the surface of fluorophor particle is formed and between the adhesive layer that the surface of another fluorophor particle is formed.

10. according to wavelength conversion body according to any one of claims 1 to 9, which is characterized in that the wavelength conversion body is in table Face has planar exit facet, and at least part of the planar exit facet, which becomes, meets Ra≤0.15 μm and Rz≤0.3 μm Flat surface.

11. wavelength conversion body according to claim 10, which is characterized in that the flat surface relative to it is described it is planar go out The occupation rate for penetrating the area in face is 36%~65.5%.

12. a kind of wavelength converting member, which is characterized in that have：

Substrate；With

It is formed in the wavelength conversion body described in any one of claim 1~11 on the substrate.

13. wavelength converting member according to claim 12, which is characterized in that be arranged on the surface of a substrate One wavelength conversion body.

14. a kind of light-emitting device, which is characterized in that using described in any one of claim 1~11 wavelength conversion body or Wavelength converting member described in claim 12 or 13 obtains white light.